The reaction of non-aqueous electrolytes on the surface of the anode during the first few charging cycles results in the generation of a solid electrolyte interphase (SEI) which is critical to the performance of LIB’s, however lithium ion intercalation through the SEI and into the anode is one of the largest limitations for high rate performance.  Electrolyte additives, which result in the generation of phosphate or sulfur rich SEI’s (as opposed to the carbonate rich SEI which results from the decomposition of electrolyte solvents such as EC), have been reported to reduce cell impedance and improve high rate performance.  The novel organophosphorous additive, α, has been investigated as an anode-film forming additive, which decreases impedance.  A comparative study of LiNi_1/3Mn_1/3Co_1/3O₂/Graphite cells with the standard electrolyte and the standard electrolyte with 0.1% (wt.) of added α was conducted in order to assay the effect of the additive on cycling behavior.  Although incorporation of α does not significantly alter the cycling behavior at standard rates, cells containing α demonstrate improved capacity retention at elevated rates.  Electrochemical impedance spectroscopy reveals that the improved rate performance of cells containing electrolyte with added α is the result of a significant decrease in charge transfer resistance on the anode.  X-ray photoelectron spectroscopy reveals changes to the composition of the anode SEI upon incorporation of α, which is likely the source of improved first cycle efficiency and reduced impedance.  Incorporation of α into a standard electrolyte formulation results in improved first cycle efficiency, improved rate performance, and decreased cell impedance on the graphitic anode.